Pre-heat the oven to 350°F. Grease a 13-inch x 9-inch brownie pan with nonstick cooking spray.
Melt the chocolates and butter in the microwave, stirring every 30-60 seconds to avoid scorching. Stir until smooth and let cool.
Beat the sugar, eggs and vanilla with a standing mixer on medium speed until light in color and thick, about 5 minutes.
Add the flour and salt and mix, then add the cooled chocolate mixture and mix until combined.
Pour the batter into the prepared pan and bake for approximately 20 minutes, until moist crumbs still attach to a tester knife. Do not over-bake! Let cool completely.
For the frosting, beat the butter and peanut butter with a mixer until smooth. Add the sugar and vanilla and beat until smooth and creamy. Frost the cooled brownies in the pan and refrigerate for at least one hour.